JP2002038269A - Method for synthesizing hard carbon nitride film - Google Patents
Method for synthesizing hard carbon nitride filmInfo
- Publication number
- JP2002038269A JP2002038269A JP2000221396A JP2000221396A JP2002038269A JP 2002038269 A JP2002038269 A JP 2002038269A JP 2000221396 A JP2000221396 A JP 2000221396A JP 2000221396 A JP2000221396 A JP 2000221396A JP 2002038269 A JP2002038269 A JP 2002038269A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- plasma
- nitride film
- carbon nitride
- synthesizing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 33
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 22
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 100
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 14
- ATDGTVJJHBUTRL-UHFFFAOYSA-N cyanogen bromide Chemical compound BrC#N ATDGTVJJHBUTRL-UHFFFAOYSA-N 0.000 claims abstract description 12
- WPBXOELOQKLBDF-UHFFFAOYSA-N cyanogen iodide Chemical compound IC#N WPBXOELOQKLBDF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 230000003213 activating effect Effects 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims description 36
- 239000002994 raw material Substances 0.000 claims description 23
- -1 cyanide compound Chemical class 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000002274 desiccant Substances 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 14
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract 2
- 239000000126 substance Substances 0.000 abstract 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 150000002825 nitriles Chemical class 0.000 abstract 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 229910052786 argon Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- QPJDMGCKMHUXFD-UHFFFAOYSA-N cyanogen chloride Chemical compound ClC#N QPJDMGCKMHUXFD-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052756 noble gas Inorganic materials 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical group [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003230 hygroscopic agent Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Chemical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】切削工具、金型、耐摩耗部
品、耐腐食膜、摺動部品、記憶媒体の保護膜などに用い
られる硬質窒化炭素膜の合成技術に関する。The present invention relates to a technique for synthesizing a hard carbon nitride film used for a cutting tool, a mold, a wear-resistant part, a corrosion-resistant film, a sliding part, a protective film of a storage medium, and the like.
【０００２】[0002]
【従来の技術】ホウ素Ｂ、炭素Ｃおよび窒素Ｎの元素か
ら構成される材料は高度が高いことが知られており、そ
の代表がダイヤモンドや立方晶窒化ホウ素ｃＢＮであ
る。近年、β型の窒化珪素と同様な構造を持つ窒化炭素
Ｃ3Ｎ4がダイヤモンドより高い硬度を持つ可能性のある
ことが理論的に予測された。そこで、硬質窒化炭素膜に
関する研究が盛んに行われるようになってきた。2. Description of the Related Art It is known that a material composed of elements of boron B, carbon C and nitrogen N has a high level, and typical examples thereof are diamond and cubic boron nitride cBN. In recent years, it has been theoretically predicted that carbon nitride C 3 N 4 having a structure similar to that of β-type silicon nitride may have higher hardness than diamond. Therefore, research on hard carbon nitride films has been actively conducted.
【０００３】窒化炭素膜の合成に関する研究は物理蒸着
法（ＰＶＤ法）と化学蒸着法（ＣＶＤ法）で行われてい
る。ＰＶＤ法では炭素に窒素イオンを注入する方法や窒
素雰囲気中で炭素を蒸着する方法が試されており、ＣＶ
Ｄ法ではメタンなどの炭化水素ガスと窒素の混合ガスを
用いてダイヤモンド状炭素を合成する方法と同様な方式
で窒化炭素膜の合成が試みられている。これらの方法の
問題点は窒化炭素膜中の窒素原子と炭素原子の比すなわ
ちＮ／Ｃ比が小さいことである。Research on the synthesis of carbon nitride films has been conducted by physical vapor deposition (PVD) and chemical vapor deposition (CVD). In the PVD method, a method of implanting nitrogen ions into carbon and a method of depositing carbon in a nitrogen atmosphere have been tried.
In method D, synthesis of a carbon nitride film is attempted in a manner similar to the method of synthesizing diamond-like carbon using a mixed gas of hydrocarbon gas such as methane and nitrogen and nitrogen. The problem with these methods is that the ratio of nitrogen atoms to carbon atoms in the carbon nitride film, that is, the N / C ratio, is small.
【０００４】理論上最も硬いと言われているβ型窒化炭
素膜のＮ／Ｃ比は４／３（＝１．３３）であるのに対
し、現状の窒化炭素膜のＮ／Ｃ比は１．０以下であり、
硬度も低い。その原因はＮ／Ｃ比が小さいことからも考
えられるように、β型窒化炭素が生成されていないこと
によるものである。現状の窒化炭素膜は結晶質ではな
く、アモルファス構造を取っており、その限りにおいて
は、β型窒化炭素膜の硬度は得られないと考えられる。The N / C ratio of a β-type carbon nitride film, which is said to be the hardest in theory, is 4/3 (= 1.33), whereas the N / C ratio of the current carbon nitride film is 1 0.0 or less,
Low hardness. The reason is that β-type carbon nitride is not generated, as can be considered from the fact that the N / C ratio is small. The current carbon nitride film is not crystalline but has an amorphous structure, and it is considered that the hardness of the β-type carbon nitride film cannot be obtained.
【０００５】アモルファス状の窒化炭素膜はダイヤモン
ド状炭素膜（ＤＬＣ）と同様に表面が平滑で、ＤＬＣ膜
以上のビッカース硬度が得られると期待されており、そ
れが実現されることにより、切削工具、金型、摺動部品
などの幅広いトライボロジー分野で利用されるものと期
待されている。しかしながら、現状の窒化炭素膜はＤＬ
Ｃ膜以上の硬度が安定して得られていない。[0005] The amorphous carbon nitride film is expected to have a smooth surface similar to the diamond-like carbon film (DLC) and a Vickers hardness higher than that of the DLC film. Is expected to be used in a wide range of tribology fields such as dies, dies and sliding parts. However, the current carbon nitride film is DL
Hardness higher than that of the C film has not been stably obtained.
【０００６】従来のＰＶＤ法で合成された窒化炭素膜は
炭素の多いアモルファス状の窒化炭素あるいは窒素含有
炭素膜のような性質のものと考えられ、膜中の窒素高い
エネルギーにより膜中に進入させられたものであり、熱
的な安定性は低い。また、ＣＶＤ法で合成された窒化炭
素膜は窒素をドープしたＤＬＣの状態と考えられてお
り、炭素に対する窒素の固溶限の関係から窒素をさらに
多くドープさせることは難しい。[0006] The carbon nitride film synthesized by the conventional PVD method is considered to have properties such as amorphous carbon nitride or nitrogen-containing carbon film having a large amount of carbon. It has low thermal stability. In addition, the carbon nitride film synthesized by the CVD method is considered to be in a state of DLC doped with nitrogen, and it is difficult to dope nitrogen more in view of the solid solubility limit of nitrogen with respect to carbon.
【０００７】[0007]
【発明が解決しようとする課題】そこで、本発明者等は
特開平１１−２２９１４７号公報でシアン化合物を含む
原料ガスをプラズマ化することにより活性化し、該プラ
ズマ中またはプラズマ化されたガスの下流に置かれた基
体上に窒化炭素膜を合成する方法を提案した。これによ
り、炭素と窒素の結合したネットワークすなわちＣ−Ｎ
結合を多く形成し、窒化炭素膜の硬質化をはかった。し
かしながら、実用的な面積に硬質皮膜を安定して製造す
ることが困難であった。本発明の課題は、プラズマＣＶ
Ｄ法をベースに、硬質な窒化炭素膜の形成を安定して行
うことのできる硬質窒化炭素膜の合成方法を提供するこ
とである。Therefore, the present inventors disclosed in Japanese Patent Application Laid-Open No. H11-229147 that a raw material gas containing a cyanide compound was activated by turning it into plasma, and was activated in the plasma or downstream of the gasified plasma. We proposed a method of synthesizing a carbon nitride film on a substrate placed on a substrate. Thereby, a network in which carbon and nitrogen are bonded, that is, C—N
Many bonds were formed, and the carbon nitride film was hardened. However, it has been difficult to stably produce a hard coating in a practical area. An object of the present invention is to provide a plasma CV
An object of the present invention is to provide a method for synthesizing a hard carbon nitride film that can stably form a hard carbon nitride film based on Method D.
【０００８】[0008]
【課題を解決するための手段】本発明者等は、研究の結
果、ＣＶＤ法で合成された窒化炭素膜の硬度は原料ガス
中の水素原子の量と深く係わり、水素原子を多く含むほ
ど硬度の低いポリマー状の膜になる傾向があることが分
かった。そして、窒化炭素膜を硬質化するためには炭素
と窒素の結合したネットワークすなわちＣ−Ｎ結合を多
く形成する一方、Ｃ−Ｈ結合やＮ−Ｈ結合、即ち水素と
の結合を減らす必要があると考えた。第一にｓｐ３結合
したＣ−Ｃ結合の結合長さが０．１５４ｎｍであるのに
対し、Ｃ−Ｎ結合のそれは０．１４７ｎｍであり、Ｃ−
Ｎ結合の三次元ネットワークができればＣ−Ｃ結合が主
体であるＤＬＣ膜より緻密で高硬度な膜が得られるもの
と推定された。次に、この三次元ネットワーク形成の障
害になるのが、水素と窒素または炭素の結合またはター
ミネーションであり、これを防ぐためには原料ガスから
水素原子を除く必要があると考えた。As a result of research, the present inventors have found that the hardness of a carbon nitride film synthesized by a CVD method is deeply related to the amount of hydrogen atoms in a source gas, and the hardness increases as the number of hydrogen atoms increases. It was found that there was a tendency to be a polymer-like film having a low molecular weight. In order to harden the carbon nitride film, it is necessary to reduce the number of C—H bonds and N—H bonds, that is, the number of bonds with hydrogen, while forming a large number of carbon-nitrogen bonded networks, that is, C—N bonds. I thought. First, the bond length of the sp3-bonded CC bond is 0.154 nm, whereas that of the C—N bond is 0.147 nm.
It is presumed that if a three-dimensional network of N bonds is formed, a film having higher density and higher hardness than a DLC film mainly composed of CC bonds can be obtained. Next, it was thought that the obstacle to the formation of the three-dimensional network was the bond or termination of hydrogen and nitrogen or carbon, and it was necessary to remove hydrogen atoms from the source gas in order to prevent this.
【０００９】そこで、本発明においては、請求項１にお
いて、炭素と窒素の結合を持つシアン化合物を含む原料
ガスをプラズマ化することにより活性化し、該プラズマ
中またはプラズマ化されたガスの下流に置かれた基体上
に窒化炭素膜を合成する方法であって、基体を少なくと
も成膜初期に負電圧にバイアスすることにより硬質窒化
炭素膜を合成する方法を提供することにより上記課題を
解決した。Therefore, in the present invention, in claim 1, a raw material gas containing a cyanide compound having a bond between carbon and nitrogen is activated by turning it into plasma, and is activated or placed in the plasma or downstream of the turned gas. The above object has been achieved by providing a method for synthesizing a carbon nitride film on a substrate formed by biasing the substrate to a negative voltage at least at the initial stage of film formation to synthesize a hard carbon nitride film.
【００１０】基体（基板）にバイアス電圧を印加するこ
とにより、緻密で硬質な窒化炭素膜が生成される。ま
た、これにより生成される窒化炭素膜はＮ／Ｃ比が１．
０に達しないものの、従来のダイヤモンド状炭素膜や窒
化炭素膜を凌ぐ硬度を持つ膜を形成できる。By applying a bias voltage to the substrate, a dense and hard carbon nitride film is generated. In addition, the carbon nitride film produced thereby has an N / C ratio of 1.
Although it does not reach 0, a film having hardness higher than that of a conventional diamond-like carbon film or carbon nitride film can be formed.
【００１１】基板バイアスは高周波を基板に直接印加ま
たはプラズマ生成用高周波による間接印加が可能であ
る。また、基板と膜の密着性を高めるためには、特に成
膜初期の基板への直流電圧印加が有効であり、その目的
には直流電圧と高周波が重畳して用いられる。そこで、
請求項２においては、基体へのバイアスを高周波による
自己バイアス、直流電圧によるバイアスまたはその両者
の重畳によるバイアスとした。As the substrate bias, a high frequency can be directly applied to the substrate or indirectly applied by a high frequency for plasma generation. In order to enhance the adhesion between the substrate and the film, it is particularly effective to apply a DC voltage to the substrate at the initial stage of film formation. Therefore,
In claim 2, the bias to the base is a self-bias by a high frequency, a bias by a DC voltage, or a bias by a superposition of both.
【００１２】次に、原料ガスに水が含まれると膜の硬度
が著しく低下するという現象は試験結果からも実証され
た。これは、僅かな水分の存在でも膜中の水素含有量が
多くなるためと考えられた。原料ガスからの水分や水素
原子を減らすためには、水分や有機化合物などの含有率
の低い原料を選定することが重要である。そこで、請求
項３においては、シアン化合物を含む原料ガスをプラズ
マ化することにより活性化し、該プラズマ中またはプラ
ズマ化されたガスの下流に置かれた基体上に窒化炭素膜
を合成する方法において、水分と合わせて水素を含む原
料ガスの全構成原子に対する水素原子の比率を５％以下
とした。なお、不純物としての水分を無視した水素を含
まない原料ガスを利用した例は前述した特開平１１−２
２９１４７号公報のものでも実施している。[0012] Next, a test result demonstrated that the hardness of the film was significantly reduced when water was contained in the raw material gas. This was thought to be due to the fact that even in the presence of a small amount of water, the hydrogen content in the film increased. In order to reduce water and hydrogen atoms from the raw material gas, it is important to select a raw material having a low content of water and organic compounds. Therefore, in claim 3, a method of synthesizing a carbon nitride film on a substrate placed in a plasma or a downstream of a plasma-converted gas is activated by converting a source gas containing a cyanide into plasma. The ratio of hydrogen atoms to all constituent atoms of the raw material gas containing hydrogen together with water was set to 5% or less. Note that an example in which a raw material gas containing no hydrogen and ignoring water as an impurity is used is described in JP-A-11-21-2.
No. 29147 is also implemented.
【００１３】また、原料ガスが水分の他は水素を含まな
い場合には、水分を含むことが問題であり、本発明にお
いては、原料ガス中の水分含有率を１％以下とするのが
よい（請求項４）。また、水分については、原料ガスを
吸湿剤または水分トラップを通してから反応槽内へ供給
することにより除去できる。そこで、原料ガスの一部ま
たは全部を吸湿剤を通して反応槽内へ供給すればよい
（請求項５）。When the raw material gas does not contain hydrogen other than water, there is a problem that the raw material gas contains water. In the present invention, the water content in the raw material gas is preferably 1% or less. (Claim 4). In addition, moisture can be removed by supplying the raw material gas through a desiccant or a moisture trap and then into the reaction tank. Therefore, part or all of the raw material gas may be supplied into the reaction tank through the desiccant (claim 5).
【００１４】原料ガスから水分や、水素分子を減少さ
せ、さらに、基体に負にバイアスをかえけることによ
り、高硬度の安定した硬質窒化炭素膜が合成可能である
（請求項６）。By reducing moisture and hydrogen molecules from the raw material gas and by applying a negative bias to the substrate, a stable hard carbon nitride film having high hardness can be synthesized (claim 6).
【００１５】また、活性化されたＣＮラジカルを効率的
に生成するためには希ガスまたは希ガスと窒素ガスをシ
アン化合物ガスに添加するか、または希ガスまたは希ガ
スと窒素ガスをプラズマ化しその流れの中にシアン化合
物ガスを添加すると効果的である。窒素ガスはまた、窒
化炭素膜中のＮ／Ｃ比を高めるためにも有効である。希
ガスとしては全ての希ガスが利用可能であるが、工業的
にはアルゴンとヘリウムが経済的である。そこで、請求
項７においては、希ガスと窒素含有ガスの一種類または
二種類以上から成るプラズマガスをプラズマ化し、該プ
ラズマ中またはプラズマの下流にてシアン化合物を含む
原料ガスを混合し、該混合ガスのプラズマ中またはプラ
ズマ化されたガスの下流に置かれた基体上に窒化炭素膜
を合成するようにした。Further, in order to efficiently generate activated CN radicals, a rare gas or a rare gas and a nitrogen gas are added to a cyanide compound gas, or a rare gas or a rare gas and a nitrogen gas are converted into plasma to form an activated CN radical. It is effective to add a cyan compound gas into the stream. Nitrogen gas is also effective for increasing the N / C ratio in the carbon nitride film. As the noble gas, any noble gas can be used, but argon and helium are economical industrially. Therefore, in claim 7, a plasma gas comprising one or more of a rare gas and a nitrogen-containing gas is converted into plasma, and a raw material gas containing a cyanide compound is mixed in the plasma or downstream of the plasma. A carbon nitride film was synthesized on a substrate placed in a gas plasma or downstream of a plasmatized gas.
【００１６】また、原料ガスとなるシアン基を持つ化合
物としてはシアンのハロゲン化物などの幅広い原料が考
えられるが、工業的にはシアン化臭素ＢｒＣＮ、シアン
化ヨウ素ＩＣＮおよびシアン化塩素ＣｌＣＮが好ましい
が、シアン化塩素については取扱が難しい。そこで、請
求項８においては、シアン化合物を含む原料ガスがシア
ン化臭素およびシアン化ヨウ素の一種類または二種類、
またはシアン化臭素およびシアン化ヨウ素の一種類また
は二種類に希ガスおよび窒素ガスの一種類または二種類
を混合するようにした。As the compound having a cyano group as a raw material gas, a wide range of raw materials such as a cyanide halide can be considered, but industrially, bromine cyanide BrCN, iodine cyanide ICN and chlorine cyanide ClCN are preferable. It is difficult to handle chlorine cyanide. Therefore, in claim 8, the source gas containing a cyanide compound is one or two of bromine cyanide and iodine cyanide,
Alternatively, one or two kinds of rare gas and nitrogen gas are mixed with one or two kinds of bromine cyanide and iodine cyanide.
【００１７】反応槽内へ供給するシアン化合物ガスの流
量の全ガス流量に対する比は非常に広い範囲の値を取り
得、１〜１００％の範囲で窒化炭素膜の合成が可能であ
った。これより、希ガスと窒素ガスを合わせた流量の全
ガス流量の比は０〜９９％となるが、その中で窒素ガス
と希ガスの流量比は０〜８０％が好ましいことがわかっ
た。そこで、請求項９においては、反応槽内へ供給する
シアン化合物ガスの流量の全ガス流量に対する比は１〜
１００％であり、かつ窒素ガスと希ガスの流量比が０〜
８０％とした。The ratio of the flow rate of the cyan compound gas supplied into the reactor to the total gas flow rate can take a very wide range, and a carbon nitride film could be synthesized in the range of 1 to 100%. From this, it was found that the ratio of the total gas flow rate of the combined flow rate of the rare gas and the nitrogen gas was 0 to 99%, and among them, the flow rate ratio of the nitrogen gas and the rare gas was preferably 0 to 80%. Therefore, in claim 9, the ratio of the flow rate of the cyan compound gas supplied into the reaction tank to the total gas flow rate is 1 to 5.
100% and the flow ratio of nitrogen gas to rare gas is 0 to
80%.
【００１８】なお、ガスの活性化手段としてはプラズマ
を生成する全ての手段が利用可能であるが、工業的には
マイクロ波、高周波、交流放電、直流放電の一種または
二種、およびそれらと磁場の併用が一般的であり利用し
やすい。また、反応圧力すなわち反応槽内の圧力も幅広
い範囲が利用可能であるが、その範囲はプラズマ発生手
段によって決まり、マイクロ波と磁場を併用して用いる
いわゆるＥＣＲプラズマの場合には約０．０００１Ｐａ
の低圧までプラズマの発生が可能であり、直流または交
流放電を用いる場合には常圧まで可能であるが実用的に
は１０ｋＰａ以下が好ましい。As a means for activating the gas, any means for generating plasma can be used. However, industrially, one or two kinds of microwave, high frequency, AC discharge and DC discharge, and a magnetic field are used. Is common and easy to use. A wide range of reaction pressure, that is, the pressure in the reaction tank, can be used, but the range is determined by the plasma generating means. In the case of so-called ECR plasma using a microwave and a magnetic field in combination, about 0.0001 Pa
Can be generated up to a low pressure, and when a DC or AC discharge is used, it can be up to normal pressure, but practically, it is preferably 10 kPa or less.
【００１９】[0019]
【発明の実施の形態】（実施例１）図１に示す装置を用
いて本発明の第１例の実施を行なった。本装置では、電
磁石３を備えたプラズマ生成室２にマイクロ波電源１２
を用いてアルゴンガス中にプラズマ１０を生成し、その
プラズマをプラズマ生成室から引き出して反応室１へ導
き、該反応室内で、原料ガス７をプラズマ１０中に導入
して励起せしめ、この励起された混合ガス２０の流れの
下流に基板支持台４上に置かれた基板５上に窒化炭素被
膜２１を合成する。本第１例の実施においては、まず、
ターボ分子ポンプ１３とロータリーポンプ１５を用い
て、プラズマ生成室２と反応槽１を０．０００１Ｐａま
で真空排気する。次に、バルブ９を開放し、プラズマガ
スであるアルゴン１１を乾燥室８内に充填された五酸化
燐を通して１０ｓｃｃｍの流量でプラズマ室２へ導入す
る。次いで、マイクロ波発振器１２から２．４５ＧＨ
ｚ、２５０Ｗのマイクロ波を投入し、ＥＣＲ条件が成立
するように設置された電磁石３を用いてプラズマ生成室
２内にプラズマ１０を発生させた。(Embodiment 1) The first embodiment of the present invention was carried out using the apparatus shown in FIG. In this apparatus, a microwave power source 12 is provided in a plasma generation chamber 2 having an electromagnet 3.
Is used to generate plasma 10 in argon gas, and the plasma is drawn out of the plasma generation chamber and led to reaction chamber 1, in which raw material gas 7 is introduced into plasma 10 to be excited. A carbon nitride film 21 is synthesized on the substrate 5 placed on the substrate support 4 downstream of the flow of the mixed gas 20. In the implementation of the first example, first,
The plasma generation chamber 2 and the reaction tank 1 are evacuated to 0.0001 Pa using the turbo molecular pump 13 and the rotary pump 15. Next, the valve 9 is opened, and argon 11 as a plasma gas is introduced into the plasma chamber 2 at a flow rate of 10 sccm through phosphorus pentoxide filled in the drying chamber 8. Next, 2.45 GH from the microwave oscillator 12
A microwave of z, 250 W was applied, and plasma 10 was generated in the plasma generation chamber 2 using the electromagnet 3 installed so as to satisfy the ECR condition.
【００２０】これにより生成されたプラズマ１０は反応
室１へと流れる。バルブ９’を開放し、反応室１のプラ
ズマ１０の流れ内に五酸化燐を充填した乾燥室８’を通
してシアン化臭素（原料ガス）７を１ｓｃｃｍの流量で
供給した。超硬合金基板５をその混合ガス２０の流れの
下流側に置き、基板には高周波電源６より高周波電力を
印加し、バイアス電圧を０〜−６０Ｖの範囲で変化さ
せ、基板上に窒化炭素膜２１を生成させた。このときの
反応槽（反応室１及びプラズマ室２）の圧力は１Ｐａで
あった。なお、ターボ分子ポンプ１３の後側のトラップ
１４は未分解のシアン化臭素をトラップする作用とロー
タリーポンプ１５からの水分の逆流を防止する役割を担
っている。The generated plasma 10 flows into the reaction chamber 1. The valve 9 'was opened, and bromine cyanide (raw material gas) 7 was supplied at a flow rate of 1 sccm through a drying chamber 8' filled with phosphorus pentoxide in the flow of the plasma 10 in the reaction chamber 1. The cemented carbide substrate 5 is placed on the downstream side of the flow of the mixed gas 20, high frequency power is applied to the substrate from the high frequency power source 6, the bias voltage is changed in the range of 0 to −60 V, and the carbon nitride film is formed on the substrate. 21 was generated. At this time, the pressure in the reaction tank (reaction chamber 1 and plasma chamber 2) was 1 Pa. The trap 14 on the rear side of the turbo molecular pump 13 has a function of trapping undecomposed bromine cyanide and a role of preventing backflow of water from the rotary pump 15.
【００２１】これにより合成された膜の硬度をマイクロ
硬度計で調べたところ、バイアス電圧０〜−６０Ｖの変
化に対して１０〜５０ＧＰａでほぼ比例関係で変化し
た。その膜についての組成をＸＰＳで分析したところ窒
素と炭素の比すなわちＮ／Ｃ比は０．３であった。図２
には本第１例の実施により得られたバイアス電圧と膜の
硬度の関係を示す。これより、硬度はバイアス電圧が負
側になるに従って高くなる比例関係があり、基板バイア
ス電圧を変化させることにより、幅広い範囲の硬質窒化
炭素膜が得られることがわかる。When the hardness of the film thus synthesized was examined with a micro hardness tester, the hardness was changed in a substantially proportional relationship at 10 to 50 GPa with respect to the change of the bias voltage of 0 to -60 V. When the composition of the film was analyzed by XPS, the ratio of nitrogen to carbon, that is, the N / C ratio was 0.3. FIG.
Shows the relationship between the bias voltage and the hardness of the film obtained by the implementation of the first example. This shows that the hardness has a proportional relationship that increases as the bias voltage becomes negative, and that a wide range of hard carbon nitride films can be obtained by changing the substrate bias voltage.
【００２２】（実施例２）次に、図３に示す装置を用い
て本発明の第２例の実施を行なった。すなわち、反応槽
（反応室）１をターボ分子ポンプ１３、トラップ１４及
びロータリーポンプ１５により０．０００１Ｐａまで真
空排気した後、反応容器内に希ガスとしてアルゴンガス
１１を３０ｓｃｃｍ、原料ガスとしてシアン化臭素７を
１０ｓｃｃｍの流量で流し、その混合ガス２０中に高周
波発振器１７からマッチングボックス１８を通して高周
波アンテナ１９に１３．５６ＭＨｚ、１００Ｗの高周波
を導入し、反応槽１内にプラズマを発生せしめた。そし
て、プラズマのガスの流れの下流側に単結晶シリコン基
板５を置き、基板上に窒化炭素膜２１を生成した。この
とき、シリコン基板５には直流電源１６を用いて負の電
圧を印加した。直流電圧１６は蒸着開始後１０分間まで
−３００Ｖを印加し、その後は電源を切り離して高周波
電力による自己バイアスを印加した。また、アルゴンガ
ス１１およびシアン化臭素７ともに五酸化燐を充填した
乾燥室８，８’をバルブ９，９’通して供給した。反応
槽内の圧力１Ｐａ、基板温度約２００゜Ｃの条件下で１
時間の生成を行った。(Embodiment 2) Next, a second embodiment of the present invention was carried out using the apparatus shown in FIG. That is, the reaction tank (reaction chamber) 1 is evacuated to 0.0001 Pa by a turbo molecular pump 13, a trap 14, and a rotary pump 15, and then 30 sccm of argon gas 11 as a rare gas and bromine cyanide as a source gas are introduced into the reaction vessel. 7 was flowed at a flow rate of 10 sccm, and a high frequency of 13.56 MHz and 100 W was introduced into the mixed gas 20 from the high frequency oscillator 17 through the matching box 18 to the high frequency antenna 19 to generate plasma in the reaction tank 1. Then, the single crystal silicon substrate 5 was placed on the downstream side of the flow of the plasma gas, and a carbon nitride film 21 was formed on the substrate. At this time, a negative voltage was applied to the silicon substrate 5 using the DC power supply 16. As the DC voltage 16, -300 V was applied until 10 minutes after the start of vapor deposition. Thereafter, the power supply was cut off, and a self-bias by high frequency power was applied. Further, the drying chambers 8, 8 'filled with phosphorus pentoxide together with the argon gas 11 and the bromine cyanide 7 were supplied through valves 9, 9'. The pressure is 1 Pa in the reactor and the substrate temperature is about 200 ° C.
Time generation was performed.
【００２３】これにより膜厚が約１μｍ窒化炭素膜２１
が得られ、膜の組成比すなわちＮ／Ｃ比は０．４であ
り、硬度は３０ＧＰａであった。Ｘ線回折にて結晶性を
調べたところアモルファス的な硬質膜であることがわか
った。図４には膜の結合状態を調べるため、フーリエ変
換型赤外分光分析（ＦＴＩＲ）により測定したデータを
示した。図４には本発明の膜の他に、水素を含むガスか
ら合成された膜および基板バイアスを印加せずに合成し
た膜のデータも示した。これによれば、比較例である水
素含有膜は剥離し、そのピークはＣ＝Ｃ結合、Ｃ＝Ｎ結
合である。また、基板バイアスのないものではその硬度
は６〜１０ＧＰａと低く、そのピークは同様にＣ＝Ｃ、
Ｃ＝Ｎ結合である。これに対して本発明の方法により得
られる窒化炭素膜は硬度３０ＧＰａと高硬度を示し、そ
の窒素と炭素の結合もＣ−Ｎ結合がピークとなり、その
量も最も多く、本発明による窒化炭素膜は本発明者らが
期待した通りの組成と高い硬度を持つ膜であることが判
る。Thus, the carbon nitride film 21 having a thickness of about 1 μm
Was obtained, the composition ratio of the film, that is, the N / C ratio was 0.4, and the hardness was 30 GPa. Examination of the crystallinity by X-ray diffraction showed that the film was an amorphous hard film. FIG. 4 shows data measured by Fourier transform infrared spectroscopy (FTIR) to check the bonding state of the film. FIG. 4 also shows data of a film synthesized from a gas containing hydrogen and a film synthesized without applying a substrate bias, in addition to the film of the present invention. According to this, the hydrogen-containing film of the comparative example was peeled off, and the peaks were C = C bonds and C = N bonds. In the case where there was no substrate bias, the hardness was as low as 6 to 10 GPa, and the peaks were similarly C = C,
C = N bond. On the other hand, the carbon nitride film obtained by the method of the present invention shows a high hardness of 30 GPa, the bond between nitrogen and carbon peaks at the CN bond, and the amount thereof is the largest. Is a film having the composition and high hardness expected by the present inventors.
【００２４】（実施例３）さらにまた、図１に示した装
置を用いて本発明の第３例の実施を行なった。実施の手
順は実施例１と同様であるが、原料ガス７として、シア
ン化臭素に替えて、シアン化ヨウ素を用い、シアン化ヨ
ウ素のキャリアガスとして窒素ガスを流した。この場合
も全てのガスは乾燥室８，８’に設けられた五酸化燐の
乾燥剤を通して、プラズマ生成室２ならびに反応室１へ
導入した。プラズマ生成室２へ供給するアルゴンガス１
１の流量は１０ｓｃｃｍ、窒素ガスの流量は３ｓｃｃｍ
であり、シアン化ヨウ素７は窒素ガスに飽和された状態
で窒素ガスとともに反応室へ供給される。次いで、マイ
クロ波電源１２から２．４５ＧＨｚ、２５０Ｗのマイク
ロ波を投入し、ＥＣＲ条件が成立するように設置された
電磁石を用いてプラズマ室２内にプラズマ１０を発生さ
せ、プラズマ化されたガスの下流に置かれたシリコン基
板５の表面に窒化炭素膜２１を合成した。シリコン基板
５には高周波電源６より高周波電力を印加し、バイアス
電圧を−４０Ｖとして４時間の生成を行った。(Embodiment 3) Further, the third embodiment of the present invention was carried out using the apparatus shown in FIG. The procedure was the same as in Example 1, except that iodine cyanide was used as the source gas 7 instead of bromine cyanide, and nitrogen gas was flowed as the carrier gas for iodine cyanide. Also in this case, all the gases were introduced into the plasma generation chamber 2 and the reaction chamber 1 through the desiccant of phosphorus pentoxide provided in the drying chambers 8, 8 '. Argon gas 1 to be supplied to plasma generation chamber 2
The flow rate of 1 is 10 sccm, and the flow rate of nitrogen gas is 3 sccm
The iodine cyanide 7 is supplied to the reaction chamber together with the nitrogen gas in a state saturated with the nitrogen gas. Next, a microwave of 2.45 GHz and 250 W is supplied from the microwave power supply 12 to generate a plasma 10 in the plasma chamber 2 using an electromagnet installed so as to satisfy the ECR condition. A carbon nitride film 21 was synthesized on the surface of the silicon substrate 5 placed downstream. High-frequency power was applied to the silicon substrate 5 from a high-frequency power supply 6 and the bias voltage was set to -40 V, and generation was performed for 4 hours.
【００２５】これにより生成された膜の硬度をマイクロ
硬度計で調べたところ、４５ＧＰａであった。その膜に
ついての組成をＸＰＳで分析したところ窒素と炭素の比
すなわちＮ／Ｃ比は０．４であった。なお、バイアス電
圧はガス圧力や種類、温度、基板電流などの様々な要因
に左右され使用するシステムにより適宜選択するのはい
うまでもない。When the hardness of the film thus formed was examined with a micro hardness tester, it was 45 GPa. When the composition of the film was analyzed by XPS, the ratio of nitrogen to carbon, that is, the N / C ratio was 0.4. The bias voltage depends on various factors such as gas pressure, type, temperature, and substrate current, and it is needless to say that the bias voltage is appropriately selected depending on the system used.
【００２６】[0026]
【発明の効果】本発明の方法によれば、シアン化合物を
用いて窒化炭素膜を合成する際に、全ての反応室へ供給
されるガス中の水素原子を減らし、かつ窒化炭素膜合成
中の基板に負のバイアスを印加することにより、硬度が
高く、密着性のよい窒化炭素膜を得ることが可能とな
り、ハードディスク、金型、切削工具などの耐摩耗膜へ
の応用が容易となり、産業上非常に有益である。According to the method of the present invention, when synthesizing a carbon nitride film using a cyanide compound, the number of hydrogen atoms in the gas supplied to all the reaction chambers is reduced, and during the synthesis of the carbon nitride film, By applying a negative bias to the substrate, it is possible to obtain a carbon nitride film with high hardness and good adhesion, and it is easy to apply it to wear-resistant films such as hard disks, molds, cutting tools, etc. Very informative.
【００２７】Ｎ／Ｃ比を単に増加させるのではなく、水
分又は水素原子の減少させ、Ｃ−Ｈ結合やＮ−Ｈ結合を
減らし、Ｃ−Ｎ結合を増加するようにしたので、Ｎ／Ｃ
比が１に満たなくても、安定した高硬度の硬質窒化炭素
膜の製造が可能となった。さらに、基板バイアスと硬度
とがほぼ比例関係をもつので、バイアス電圧を制御する
ことにより、幅広い範囲の硬質窒化炭素膜が得られ、さ
らには任意の硬度の硬質窒化炭素膜を容易に得られ、よ
り安定した硬質窒化炭素膜の製造が可能なものとなっ
た。Instead of simply increasing the N / C ratio, the N / C ratio was reduced by reducing the amount of water or hydrogen atoms, reducing the number of CH bonds and NH bonds, and increasing the number of CN bonds.
Even if the ratio is less than 1, stable hard carbon nitride film having high hardness can be manufactured. Further, since the substrate bias and the hardness have a substantially proportional relationship, by controlling the bias voltage, a wide range of hard carbon nitride films can be obtained, and a hard carbon nitride film of any hardness can be easily obtained. A more stable hard carbon nitride film can be manufactured.
【図１】本発明の第１及び第３の実施の形態に用いた装
置の概略説明図である。FIG. 1 is a schematic explanatory view of an apparatus used in first and third embodiments of the present invention.
【図２】本発明の第１の実施の形態におけるバイアス電
圧と窒化炭素膜の硬度の関係を示す図である。FIG. 2 is a diagram showing a relationship between a bias voltage and a hardness of a carbon nitride film according to the first embodiment of the present invention.
【図３】本発明の第２の実施の形態に用いた装置の概略
説明図である。FIG. 3 is a schematic explanatory view of an apparatus used in a second embodiment of the present invention.
【図４】本発明の第２の実施の形態における本発明の膜
ならびに比較例として測定された膜のＦＴＩＲスペクト
ルを示す図である。FIG. 4 is a diagram showing FTIR spectra of a film of the present invention and a film measured as a comparative example in the second embodiment of the present invention.
１ 反応室（反応槽） ２ プラズマ生成室 ５ 基体（基板） ６ 高周波電源 ７ シアン化合物（原料ガス） ８、８’ 乾燥室（吸湿剤） １０ プラズマ １１ 希ガス（アルゴンガス） １６ 直流電源 ２０ 混合ガス（プラズマ混合ガス） ２１ 窒化炭素膜 DESCRIPTION OF SYMBOLS 1 Reaction chamber (reaction tank) 2 Plasma generation chamber 5 Base (substrate) 6 High frequency power supply 7 Cyanide compound (raw material gas) 8, 8 'Drying chamber (hygroscopic agent) 10 Plasma 11 Rare gas (Argon gas) 16 DC power supply 20 Mixing Gas (plasma mixed gas) 21 Carbon nitride film
───────────────────────────────────────────────────── フロントページの続き (72)発明者 斎藤 秀俊 新潟県長岡市深沢町1769番地１ (72)発明者 神田 一隆 富山県富山市不二越本町一丁目１番１号 株式会社不二越内 Ｆターム(参考） 4K030 AA02 AA17 AA24 BA27 BA38 EA03 FA01 FA04 JA06 KA20 LA21 LA22 LA23 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hidetoshi Saito 1769-1, Fukasawa-cho, Nagaoka-shi, Niigata (72) Inventor Kazutaka Kanda 1-1-1, Fujikoshi-honmachi, Toyama-shi, Toyama F-term (F-term ( Reference) 4K030 AA02 AA17 AA24 BA27 BA38 EA03 FA01 FA04 JA06 KA20 LA21 LA22 LA23
Claims (9)
化することにより活性化し、該プラズマ中またはプラズ
マ化されたガスの下流に置かれた基体上に窒化炭素膜を
合成する方法であって、前記基体は少なくとも成膜初期
に負電圧にバイアスされていることを特徴とする硬質窒
化炭素膜の合成方法。1. A method for synthesizing a carbon nitride film on a substrate placed in a plasma or downstream of a plasma-converted gas by activating a source gas containing a cyanide compound by converting the gas into plasma. A method for synthesizing a hard carbon nitride film, wherein the substrate is biased to a negative voltage at least at the beginning of film formation.
己バイアス、直流電圧によるバイアスまたはその両者の
重畳によるバイアスであることを特徴とする請求項１記
載の硬質窒化炭素膜の合成方法。2. The method for synthesizing a hard carbon nitride film according to claim 1, wherein the bias to the base is a self-bias by a high frequency, a bias by a DC voltage, or a bias by a superposition of both.
プラズマ化することにより活性化し、該プラズマ中また
はプラズマ化されたガスの下流に置かれた基体上に窒化
炭素膜を合成する方法であって、前記原料ガスの全構成
原子に対する水素原子の比率が５％以下であることを特
徴とする硬質窒化炭素膜の合成方法。3. A method of activating a source gas containing a cyanide compound and hydrogen by turning it into plasma, and synthesizing a carbon nitride film on a substrate placed in the plasma or downstream of the plasmated gas. A ratio of hydrogen atoms to all constituent atoms of the source gas is 5% or less.
化することにより活性化し、該プラズマ中またはプラズ
マ化されたガスの下流に置かれた基体上に窒化炭素膜を
合成する方法であって、前記原料ガス中の水分含有率が
１％以下であることを特徴とする硬質窒化炭素膜の合成
方法。4. A method for synthesizing a carbon nitride film on a substrate placed in a plasma or downstream of a plasma-converted gas by activating the source gas containing a cyanide compound by converting the gas into plasma. A method for synthesizing a hard carbon nitride film, wherein the raw material gas has a water content of 1% or less.
化することにより活性化し、該プラズマ中またはプラズ
マ化されたガスの下流に置かれた基体上に窒化炭素膜を
合成する方法であって、前記原料ガスの一部または全部
を吸湿剤を通して反応槽内へ供給することを特徴とする
硬質窒化炭素膜の合成方法。5. A method of activating a source gas containing a cyanide compound by converting it into a plasma, and synthesizing a carbon nitride film on a substrate placed in the plasma or downstream of the plasmatized gas. A method for synthesizing a hard carbon nitride film, characterized in that part or all of a raw material gas is supplied into a reaction tank through a desiccant.
ずれか一に記載の原料ガスであることを特徴とする請求
項１又は２記載の硬質窒化炭素膜の合成方法。6. The method for synthesizing a hard carbon nitride film according to claim 1, wherein the source gas is the source gas according to any one of claims 3 to 5.
種類以上から成るプラズマガスをプラズマ化し、該プラ
ズマ中またはプラズマの下流にてシアン化合物を含む原
料ガスを混合し、該混合ガスのプラズマ中またはプラズ
マ化されたガスの下流に置かれた基体上に窒化炭素膜を
合成することを特徴とする請求項１乃至６のいずれか一
に記載の硬質窒化炭素膜の合成方法。7. A plasma gas comprising one or more of a rare gas and a nitrogen-containing gas is converted into plasma, and a raw material gas containing a cyanide compound is mixed in or downstream of the plasma, and the plasma of the mixed gas is mixed. The method for synthesizing a hard carbon nitride film according to any one of claims 1 to 6, wherein the carbon nitride film is synthesized on a substrate placed in the middle or downstream of the plasmatized gas.
臭素およびシアン化ヨウ素の一種類または二種類、また
はシアン化臭素およびシアン化ヨウ素の一種類または二
種類に希ガスおよび窒素ガスの一種類または二種類を混
合したものであることを特徴とする請求項１乃至７のい
ずれか一に記載の硬質窒化炭素膜の合成方法。8. A raw material gas containing a cyanide compound is one or two kinds of bromine cyanide and iodine cyanide, or one kind or two kinds of bromine cyanide and iodine cyanide and one kind of a rare gas and nitrogen gas or The method for synthesizing a hard carbon nitride film according to claim 1, wherein the two types are mixed.
流量の全ガス流量に対する比は１〜１００％であり、か
つ窒素ガスと希ガスの流量比が０〜８０％であることを
特徴とする請求項１乃至８のいずれか一に記載の硬質窒
化炭素膜の合成方法。9. The method according to claim 1, wherein the ratio of the flow rate of the cyan compound gas supplied to the reaction vessel to the total gas flow rate is 1 to 100%, and the flow rate ratio of the nitrogen gas to the rare gas is 0 to 80%. The method for synthesizing a hard carbon nitride film according to claim 1.
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Cited By (7)
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|---|---|---|---|---|
| RU2288170C2 (en) * | 2005-02-16 | 2006-11-27 | Карбодеон Лтд Ой | Carbon nitride preparation method |
| JP2008229781A (en) * | 2007-03-20 | 2008-10-02 | Osg Corp | Hard film and tool coated with hard film |
| JP2008229782A (en) * | 2007-03-20 | 2008-10-02 | Osg Corp | Hard film and tool coated with hard film |
| JP2014114492A (en) * | 2012-12-11 | 2014-06-26 | Yuutekku:Kk | Plasma cvd apparatus, and manufacturing method of magnetic recording media |
| JPWO2013061398A1 (en) * | 2011-10-24 | 2015-04-02 | 株式会社ユーテック | CxNyHz film, film forming method, magnetic recording medium, and manufacturing method thereof |
| WO2015047919A1 (en) | 2013-09-30 | 2015-04-02 | Dow Global Technologies Llc | Polyester polyol and polyol blends and rigid polyurethane foam manufacturing |
| JP2018048410A (en) * | 2017-12-04 | 2018-03-29 | 株式会社ユーテック | CxNyHz FILM, FILM DEPOSITION METHOD, MAGNETIC RECORDING MEDIUM, AND PRODUCTION METHOD THEREOF |
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| JPH03240959A (en) * | 1990-02-16 | 1991-10-28 | Sumitomo Electric Ind Ltd | Method for synthesizing carbon nitride thin film |
| JPH08319568A (en) * | 1995-05-25 | 1996-12-03 | Kiichiro Kamata | Production of hard nitrogen-containing carbon film |
| JPH11229147A (en) * | 1998-02-19 | 1999-08-24 | Nachi Fujikoshi Corp | Method for synthesizing hard carbon nitride film |
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|---|---|---|---|---|
| JPH03240959A (en) * | 1990-02-16 | 1991-10-28 | Sumitomo Electric Ind Ltd | Method for synthesizing carbon nitride thin film |
| JPH08319568A (en) * | 1995-05-25 | 1996-12-03 | Kiichiro Kamata | Production of hard nitrogen-containing carbon film |
| JPH11229147A (en) * | 1998-02-19 | 1999-08-24 | Nachi Fujikoshi Corp | Method for synthesizing hard carbon nitride film |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2288170C2 (en) * | 2005-02-16 | 2006-11-27 | Карбодеон Лтд Ой | Carbon nitride preparation method |
| US7708971B2 (en) | 2005-02-16 | 2010-05-04 | Carbodeon Ltd Oy | Method for preparing carbon nitride C3N4 |
| JP2008229781A (en) * | 2007-03-20 | 2008-10-02 | Osg Corp | Hard film and tool coated with hard film |
| JP2008229782A (en) * | 2007-03-20 | 2008-10-02 | Osg Corp | Hard film and tool coated with hard film |
| JPWO2013061398A1 (en) * | 2011-10-24 | 2015-04-02 | 株式会社ユーテック | CxNyHz film, film forming method, magnetic recording medium, and manufacturing method thereof |
| US9524742B2 (en) | 2011-10-24 | 2016-12-20 | Youtec Co., Ltd. | CXNYHZ film, deposition method, magnetic recording medium and method for manufacturing the same |
| JP2014114492A (en) * | 2012-12-11 | 2014-06-26 | Yuutekku:Kk | Plasma cvd apparatus, and manufacturing method of magnetic recording media |
| WO2015047919A1 (en) | 2013-09-30 | 2015-04-02 | Dow Global Technologies Llc | Polyester polyol and polyol blends and rigid polyurethane foam manufacturing |
| JP2018048410A (en) * | 2017-12-04 | 2018-03-29 | 株式会社ユーテック | CxNyHz FILM, FILM DEPOSITION METHOD, MAGNETIC RECORDING MEDIUM, AND PRODUCTION METHOD THEREOF |
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